Azo dyestuffs containing fluorotriazinyl and vinylsulfonylmethyl-type reactive groups
Reactive dyestuffs which, as the free acid, have the following formula ##STR1## in which K is ##STR2## the bonding to the triazinyl radical taking place in each case via the amino function of K, and the remaining substituents have the meaning given in the description, are suitable in particular for the dyeing and printing of natural and synthetic OH- and/or amido-containing materials.
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The invention relates to new azo reactive dyestuffs containing a monofluorotriazinyl and vinylsulphonyl reactive radical. It is true that combinations of reactive components are disclosed in EP-A-94,055, EP-A-85,025, EP-A-65,732, US-A-4,730,038 and EP-A-307,817, but this prior art still presents problems in terms of practical application.
The present invention relates to mono and disazo reactive dyestuffs which, as the free acid, have the formula (1) ##STR3## in which Y denotes CH.dbd.CH.sub.2, CH.sub.2 CH.sub.2 OSO.sub.3 H or CH.sub.2 CH.sub.2 Cl,
R denotes H or C.sub.1 -C.sub.3 -alkyl, which may be substituted by OH, CO.sub.2 H or CN, in particular CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, CH.sub.2 CH.sub.2 OH, CH.sub.2 CH.sub.2 CO.sub.2 H, CH.sub.2 CO.sub.2 H or CH.sub.2 CH.sub.2 CN,
Z denotes H, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, in particular CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5 or OC.sub.3 H.sub.7, and
D denotes a phenyl or naphthyl radical substituted by SO.sub.3 H, CO.sub.2 H, CH.sub.2 --SO.sub.2 W, SO.sub.2 W, NH--COCH.sub.3, C.sub.1 -C.sub.4 -alkyl and/or C.sub.1 -C.sub.4 -alkoxy, W having one of the meanings given under Y, or denotes a radical of the structure ##STR4## K denotes ##STR5## the bonding to the triazinyl radical taking place in each case via the amino function of K,
A denotes H, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,
B denotes H, C.sub.1 -C.sub.4 -alkyl, halogen, C.sub.1 -C.sub.4 -alkoxy, OH--, SO.sub.3 H- or OSO.sub.3 H-substituted C.sub.1 -C.sub.4 -alkyl, NHCONH.sub.2, NHCO-(-C.sub.1 -C.sub.4 -alkyl), NHCOCH.sub.2 OSO.sub.3 H, NHCO-(--CH.sub.2 --).sub.1-3 SO.sub.3 H, NHCOCH.sub.2 OH or NHCO-(--O-C.sub.1 -C.sub.4 -alkyl).
Preferred representatives of the formula (1) in which K is ##STR6## are dyestuffs of the formula (2) ##STR7## in which R, Y and Z have the abovementioned meaning and the phenyl or naphthyl radical D can be additionally substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, NHCOCH.sub.3, CH.sub.2 SO.sub.2 W or SO.sub.2 W, W having one of the meanings given under Y.
Particular preference is given to dyestuffs, in particular, of the formula (2) in which D represents a radical of the formula (3) and (4). ##STR8##
Particular preference is also given to dyestuffs of the formula (5) and (6) ##STR9## in which V denotes H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 or NHAcyl, in particular NH--CO--CH.sub.3,
p,m, independently of one another, denote 0 or 1,
R denotes H or C.sub.2 H.sub.5,
W,Y, independently of one another, denote CH.dbd.CH.sub.2 or CH.sub.2 CH.sub.2 OSO.sub.3 H, and
Z denotes H, CH.sub.3 or OCH.sub.3
Very particular preference is given to dyestuffs of the formula (7) and (8) ##STR10## in which p,m, independently of one another, denote 0 or 1,
R denotes H or C.sub.2 H.sub.5,
Y denotes CH.dbd.CH.sub.2 or CH.sub.2 CH.sub.2 OSO.sub.3 H,
and
Z denotes H, CH.sub.3 or OCH.sub.3.
Preferred representatives of the formula (1) in which K is ##STR11## are dyestuffs of the formula (9) ##STR12## in which A, B, R, Y and Z have the meanings mentioned for formula (1).
The phenyl or naphthyl radical D can be additionally substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, NHCOCH.sub.3, CH.sub.2 SO.sub.2 W or SO.sub.2 W.
Particular preference is given to dyestuffs of the formulae (10) and (11) ##STR13## in which X denotes H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 SO.sub.2 W or SO.sub.2 W, and
A, B, R, W and Z have the meanings given for formula (1), B in formula (10) representing in particular H, CH.sub.3, C.sub.1 -C.sub.4 -alkoxy, NH--CO-(C.sub.1 -C.sub.4 -alkyl), NHCOCH.sub.2 OH, NHCOCH.sub.2 OSO.sub.3 H or NHCO(--CH.sub.2).sub.1-3 -SO.sub.3 H.
Very particular preference is given to dyestuffs of the formula (10) and (11) in which
A is H,
B is NHCOCH.sub.3, NHCONH.sub.2 or NHCOCH.sub.2 OSO.sub.3 H, in formula (10) in particular CH.sub.3, OCH.sub.3, NHCOCH.sub.3 or NHCOCH.sub.2 OSO.sub.3 H,
R is H or C.sub.2 H.sub.5,
W,Y, independently of one another, are CH.dbd.CH.sub.2 or CH.sub.2 CH.sub.2 OSO.sub.3 H, and
Z is H, CH.sub.3 or OCH.sub.3.
Formulae (1) to (11) represent the sulpho-containing dyestuffs in the form of free acids. In general, the preparation gives the salts, in particular the alkali metal salts, such as sodium salts, potassium salts or lithium salts. The dyestuffs can be obtained and used as powders or as concentrated aqueous solutions.
Preparation of the dyestuffs (1) in which K is ##STR14## is carried out, for example, by the following procedure:
Diazotisation of amines D-NH.sub.2 and coupling of the resulting diazonium compounds to aminonaphtholsulphonic acid derivatives of the formula (12). ##STR15##
The intermediates (12) are prepared, for example, condensing aminonaphtholmono- or -disulphonic acids or (aminobenzoyl)aminonaphtholmono- or -disulphonic acids at the amine function by known methods (for example EP-A-40,806, DE-A-2,711,150, EP-A-172,790 or DE-A-2,747,014) with trifluoro-s-triazine and reacting the difluorotriazinyl compounds obtained with amines of the formula (13) ##STR16## in the presence of acid-binding agents. Details of further possibilities of synthesis can be seen from Examples 1-93. Examples of aminonaphtholsulphonic acids are: ##STR17##
Examples of suitable amines of the formula (13) are: ##STR18##
Preparation of the dyestuffs (1) in which K is ##STR19## is carried out, for example, by the following procedure: 1. By condensation of trifluoro-s-triazine with a dyestuff base of the formula (14) ##STR20## in the presence of acid-binding agents, followed by a second condensation of the resulting difluorotriazine compounds of the formula (15) ##STR21## with amino compounds of the formula (13) ##STR22## 2. By condensation of trifluoro-s-triazine with amino compounds of the formula (13) in the presence of acid-binding agents, followed by a second condensation of the resulting difluorotriazine compound of the formula (16) ##STR23## with dyestuff bases of the formula (14).
Examples of dyestuff bases (14) include: ##STR24##
Suitable amines of the formula (13) have already been mentioned above by way of example.
The dyestuffs according to the invention are highly suitable for the dyeing and printing of natural and synthetic OH- and/or amido-containing materials, in particular those made of cellulose and polyamides. They are particularly suitable for the dyeing of cellulose materials, such as cotton or staple viscose, by the exhaust and cold pad-batch methods.
The dyestuffs can be used in a mixture with other dyestuffs for trichromatic dyeing.
Dyeings having good general fastness properties, in particular wetfastness properties, are obtained in combination with good build-up properties and high fixation yields.
EXAMPLE 10.1 mol of the amino compound of the formula ##STR25## is stirred and dissolved in 100 ml of water and 100 g of ice. After addition of 0.1 mol of sodium bicarbonate, 0.11 mol of trifluoro-s-triazine are added dropwise at 0.degree. C. over a period of 10 minutes. About 250 ml of an aqueous solution of the condensation product of the formula ##STR26## are obtained.
EXAMPLE 20.1 mol of 4-amino-5-hydroxy-2,7-naphthalenedisulphonic acid is suspended in 150 ml of water and dissolved under neutral conditions using a 10% strength lithium hydroxide solution. The above condensation solution (Example 1) is then added, and the pH is simultaneously maintained between 4.0 and 4.5 by addition of lithium carbonate. The second condensation is complete after about 6 hours at 10 to 20.degree. C.
0.1 mol of 2-amino-1,5-naphthalenedisulphonic acid is diazotised in a known manner, and the resulting diazonium salt mixture is added to the solution of the coupling component at pH 6.5-7.5 at 20.degree. C. Isolation and drying give about 45 g of a salt-containing red powder of the following structure ##STR27## which dyes cotton by the dyeing and printing processes customary for reactive dyestuffs in red hues. (.lambda..sub.max =517, 540 nm (H.sub.2 O)).
By varying the amine component in Example 1 and the coupling or diazo component in Example 2, further valuable red reactive dyestuffs can be obtained (see Table 1).
TABLE 1
__________________________________________________________________________
##STR28##
Position
Ex.
D SO.sub.3 H
R Z CH.sub.2 SO.sub.2 Y
__________________________________________________________________________
##STR29## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
4 " 3 C.sub.2 H.sub.5
H "
5 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub. 2 C.sub.2 H.sub.4
SO.sub.3 H
6 " 3 H 4-OCH.sub.3
"
7 " 3 H 4-CH.sub.3
"
8 " 3 C.sub.2 H.sub.5
4-OCH.sub.3
"
8a " 3 C.sub.2 H.sub.5
4-CH.sub.3
"
9
##STR30## 4 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
10 " 4 H H "
11 " 4 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
12 " 4 C.sub.2 H.sub.5
H "
13 " 3 H H 4-CH.sub.2 SO.sub.2 CHCH.sub.2
14 " 3 C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2 CHCH.sub.2
15 " 3 H H 3-CH.sub.2 SO.sub.2 CHCH.sub.2
16 " 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
Cl
17
##STR31## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
18 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
19 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
20
##STR32## 4 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
21
##STR33## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
22 " 4 H H "
23 " 3 C.sub.2 H.sub.5
H "
24 " 3 C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
25 " 3 H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
26
##STR34## 3 H H "
26a
" 3 H 4-CH.sub.3
"
27
##STR35## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
28 " 3 C.sub.2 H.sub.5
H "
29 " 3 CH.sub.2 CH.sub.2 CO.sub.2 H
H "
30 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
31 " 4 H H "
32
##STR36## 3 H H "
33 " 3 C.sub.2 H.sub.5
H "
34 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
34a
##STR37## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
34b
" 3 H 4-CH.sub.3
"
34c
" 3 C.sub.2 H.sub.5
4-CH.sub.3
"
34d
" 3 C.sub.2 H.sub.5
4-OCH.sub.3
"
35
##STR38## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
36
##STR39## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
37 " 3 C.sub.2 H.sub.5
H "
38
##STR40## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
39
##STR41## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
40 " 3 C.sub.2 H.sub.5
H "
41
##STR42## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
42
##STR43## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
43 " 3 CH.sub.2 CH.sub.2 CO.sub.2 H
H "
44
##STR44## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
45 " 2 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
46 " 3 C.sub.2 H.sub.5
H "
47 " 3 C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
OSO.sub.3 H
48 " 4 C.sub.2 H.sub.5
H "
__________________________________________________________________________
Dyestuff Examples 2 to 48 are also available by the following synthesis sequence:
First, 0.1 mol of 4-amino-5-hydroxy-2,7 (or 1,7)-naphthalenedisulphonic acid is condensed with 0.11 mol of cyanuric fluoride at 0.degree. C. and pH 4.0 to 4.5 in a known manner, and the monocondensation product is then reacted with 0.1 mol of the amine component in an increasing temperature range from 0.degree. to 20.degree. C. and at pH 4.0 to 6.5. pH control takes place by means of aqueous sodium carbonate solution or potassium bicarbonate solution. In the last step of the reaction sequence, suitable diazonium salts (0.1 mol) are then coupled to the biscondensation product at 10.degree. to 20.degree. C. and pH 6.5 to 7.5. Isolation of the dyestuffs is then carried out as described in Example 2.
Example 2 is repeated, using the corresponding N-(4-aminobenzoyl) derivatives instead of 4-amino-5-hydroxy-2,7 (or 1,7)-naphthalenedisulphonic acid, giving the following red dyestuffs:
EXAMPLE 49 ##STR45## EXAMPLE 50 ##STR46##If the above variation is carried out with Example 26, likewise a valuable red reactive dyestuff is obtained.
EXAMPLE 51 ##STR47## EXAMPLE 520.1 mol of the monoazo compound of the formula ##STR48## is dissolved under neutral conditions in 500 ml of water. The ice-cold condensation solution from Example 1 is added to this solution, and the pH is kept constant between 6.5 and 7.0 with 20% strength sodium carbonate solution. After stirring at 10.degree. to 25.degree. C. and pH 7.0 for about 6 hours, the dyestuff is precipitated by addition of common salt, isolated by suction filtration and dried, giving about 60 g of salt-containing red dyestuff powder which has the formula ##STR49## and dyes cotton in orange-red hues (485 nm). By varying the amine component in Example 1 and the coupling or diazo component in Example 52, further valuable orange and scarlet reactive dyestuffs can be obtained (Table 2).
TABLE 2
__________________________________________________________________________
##STR50##
Posi-
Ex.
D tion-NH
R Z CH.sub.2 SO.sub.2 Y
__________________________________________________________________________
53
##STR51## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
54 " 3 C.sub.2 H.sub.5
H "
55 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub. 2
H.sub.4 OSO.sub.3 H
56 " 3 H 4-OCH.sub.3
"
57 " 3 H 4-CH.sub.3
"
58
##STR52## 2 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
59 " 2 C.sub.2 H.sub.5
H "
60 " 2 C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
61
##STR53## 2 H H 4-CH.sub.2 2C.sub.2 H.sub.4
OSO.sub.3 H
62 " 2 H H 4-CH.sub.2 SO.sub.2 CHCH.sub.2
63 " 2 H H 3-CH.sub.2 SO.sub.2 CHCH.sub.2
64 " 4 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
65
##STR54## 3 H H "
66
##STR55## 3 H H "
66a
" 3 C.sub.2 H.sub.5
H "
66b
" 3 H 4-OCH.sub.3
"
67
##STR56## 2 H H "
68
##STR57## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
69 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
70 " 3 C.sub.2 H.sub.5
H "
71 " 2 C.sub.2 H.sub.5
H "
72
##STR58## 2 H H "
73
##STR59## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
74 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
75
##STR60## 3 H H "
76
##STR61## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
77 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 CHCH.sub.2
78
##STR62## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.2 H
78a
" 3 H 4-OCH.sub.3
"
78b
" 3 C.sub.2 H.sub.5
4-OCH.sub.3
"
78c
" 3 H 4-CH.sub.3
"
79 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2
H.sub.4OSO.sub.2 H
80 " 3 C.sub.2 H.sub.5
H "
81 " 3 C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2 C.sub.2
H.sub.4OSO.sub.3 H
81a
" 3 C.sub.2 H.sub.5
4-CH.sub.3
"
82
##STR63## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
83 " 3 C.sub.2 H.sub.5
H "
83a
" 3 H 4-CH.sub.3
"
83b
" 3 H 4-OCH.sub.3
"
83c
" 3 C.sub.2 H.sub.5
4-CH.sub.3
"
83d
" 3 C.sub.2 H.sub.5
4-OCH.sub.3
"
84
##STR64## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
85 " 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
86
##STR65## 3 H H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
87 " 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
88 " 3 C.sub.2 H.sub.5
H "
88a
" 3 C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2 C.sub.2 H.sub.4
SO.sub.3 H
89
##STR66## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2
H.sub.5 OSO.sub.3 H
90 " 2 H H "
91
##STR67## 3 H H "
92
##STR68## 3 H H "
93
##STR69## 3 H H 3-CH.sub.2 SO.sub.2 C.sub.2 H.sub.5
SO.sub.3 H
__________________________________________________________________________
Dyestuff Examples 52 to 93 are also available by the following synthesis sequence:
First, 0.1 mol of amino-4-hydroxy-2-naphthalenesulphonic acid is reacted with the condensation solution from Example 1 at 0.degree. C. and pH 4.5. During the reaction time of about 3 hours, it is quite possible for the reaction temperature to rise to room temperature. At pH 6.5-7.5 (sodium carbonate solution), suitable diazonium salts (0.1 mol in each case) are then coupled onto the colourless biscondensation products. The dyestuffs are isolated by salting out and suction filtration.
Dyestuff mixtures, for example a mixture of Example 2 and 3, can be obtained by using in Example 1 a mixture of two isomers, i.e., 3- and 4-[(2-sulphatoethylsulphonyl)methyl]aniline instead of 3-[(2-sulphatoethylsulphonyl)methyl]aniline.
EXAMPLE 9423.6 g of 7-amino-1,3-naphthalenedisulphonic acid monosodium salt are stirred in 150 ml of water/30 g of ice and 20 ml of concentrated hydrochloric acid, and an aqueous sodium nitrite solution is added dropwise at 5.degree. to 10.degree. C. After stirring at 5.degree. to 10.degree. C. for one hour, excess nitrous acid is removed with sulphamic acid.
This cream-coloured suspension is metered into a neutral solution of the coupling component prepared from 13.5 g of N-(3-aminophenyl)acetamide hydrochloride, 50 ml of water, 50 g of ice and about 30 ml of a 10% strength aqueous lithium hydroxide solution over a period of 30 minutes. During this addition, the pH of the reaction mixture is kept constant at 6.0 to 6.5 with 20% strength aqueous potassium bicarbonate solution at a maximum temperature of 10.degree. C. After addition is complete, stirring is continued for 30 minutes, during which the pH is still kept constant.
Ice is now added to this orange-coloured coupling solution until a temperature of 0.degree. C. is reached. 12 g of cyanuric fluoride are swiftly added, and the pH is simultaneously kept constant at 6.0 to 6.2 by addition of a 20% strength potassium bicarbonate solution. Condensation is complete after 10 minutes. A neutral solution of 21.5 g of 3-[(2-sulfatoethylsulfonyl)methyl]aniline in 100 ml of water is now slowly metered into this mixture while keeping the pH constant at 6.5 to 7.0 by addition of 20% strength sodium carbonate solution. The reaction mixture is then warmed to 20.degree. C. over a period of 2 hours and with further pH control (6.5 to 7.0). Isolation and drying give 65 g of an orange-red powder (.lambda..sub.max =389 nm (H.sub.2 O)) of the structure ##STR70## which dyes cotton in reddish yellow hues.
The same dyestuff is also obtained by first condensing 11 g of cyanuric fluoride with 21.5 g of 3-[(2-sulphatoethylsulphonyl)methyl]aniline in 150 ml of water/50 g of ice at 0.degree. C. at a constant pH of 6.0, and reacting the resulting condensation product with the abovementioned coupling solution.
By varying the diazo component D-NH.sub.2, the aniline coupling component containing A and B and the amino compound of the sulphonylmethyl structure, further valuable reactive dyestuffs of the formula ##STR71## for example those of the table below, can be obtained analogously to Example 94.
Dyestuff mixtures, for example a mixture of Example 1 and 3, can be obtained by using in Example 1 a mixture of the two isomers, i.e., 3- and 4-[(2-sulphatoethylsulphonyl)methyl]aniline instead of 3-[(2-sulphatoethylsulphonyl)methyl]aniline.
__________________________________________________________________________
Ex.
D B A R Z CH.sub.2 SO.sub.2
__________________________________________________________________________
Y
95
##STR72## NHCOCH.sub.3
H C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
96 " " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
97 " " H C.sub.2 H.sub.5
H "
98 " " OCH.sub.3
C.sub.2 H.sub.5
H "
99 " NHCOCH.sub.2 OSO.sub.3 H
H H H 3-CH.sub.2 SO.sub.2
CHCH.sub.2
100
" NHCOCH.sub.3
H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
101
" NHCONH.sub.2
H C.sub.2 H.sub.5
H "
102
" CH.sub.3 H H H 4-CH.sub.2 SO.sub.2
C.sub.2
H.sub.4 OSO.sub.3 H
103
" H OCH.sub.3
C.sub.2 H.sub.5
H "
104
" NHCOCH.sub.2 OH
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
105
##STR73## NHCOCH.sub.3
H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
106
" " H C.sub.2 H.sub.5
H "
107
" " H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
108
" " H H H "
109
" OCH.sub.3 OCH.sub.3
H H "
110
" NHCONH.sub.2
H C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
111
##STR74## NHCOCH.sub.3
H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
112
" " H H 4-OCH.sub.3
"
113
" " H C.sub.2 H.sub.5
H "
114
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
115
##STR75## NHCOCH.sub.3
H C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
116
" NHCONH.sub.2
H C.sub.2 H.sub.5
H "
117
" " H H H "
118
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
119
" " H C.sub.2 H.sub.5
H "
120
" " H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
CHCH.sub.2
121
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub. 4
OSO.sub.3 H
122
##STR76## NHCOCH.sub.3
H C.sub.2 H.sub.5
H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
123
" NHCOCH.sub.2 OSO.sub.3 H
H H H "
124
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
125
" NHCOC.sub.2 H.sub.4 SO.sub.3 H
H C.sub.2 H.sub.5
H "
126
##STR77## OCH.sub.3 H CH.sub.2 CH.sub.2 CO.sub.2 H
H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
127
" CH.sub.2 SO.sub.3 H
H H H "
128
##STR78## NHCOCH.sub.3
H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
129
" " H C.sub.2 H.sub.5
H "
130
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
131
" NHCONH.sub.2
H H H "
132
" " H C.sub.2 H.sub.5
H "
133
" " H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
134
" " H H H "
135
##STR79## NHCONH.sub.2
H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
136
" " H H 4-OCH.sub.3
"
137
" " H C.sub.2 H.sub.5
H "
138
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
139
" NHCOCH.sub.3
H H H "
140
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
141
" " H C.sub.2 H.sub.5
H "
142
##STR80## NHCONH.sub.2
H H H "
143
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
144
" " H C.sub.2 H.sub.5
H "
145
##STR81## NHCOCH.sub.3
H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
146
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
147
" NHCONH.sub.2
H C.sub.2 H.sub.5
H "
148
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.
3 H
149
##STR82## NHCOCH.sub.3
H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
150
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
151
" NHCONH.sub.2
H C.sub.2 H.sub.5
H "
152
" " H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
153
" OCH.sub.3 OCH.sub.3
H H "
154
##STR83## NHCOCH.sub.2 OSO.sub.3 H
H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
155
" " H C.sub.2 H.sub.5
H "
156
" NHCOCH.sub.2 CH.sub.2 SO.sub.3 H
H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
157
" CH.sub.2 SO.sub.3 H
H C.sub.2 H.sub.5
H "
158
##STR84## NHCOCH.sub.2 OSO.sub.3 H
H H H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
159
" " H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
160
##STR85## " H H H "
161
##STR86## NHCOCH.sub.3
H H 4-CH.sub.3
"
162
##STR87## NHCOCH.sub.3
H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
163
" NHCOCH.sub.3
H C.sub.2 H.sub.5
4-CH.sub.3
"
164
##STR88## NHCONH.sub.2
H H H 3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
165
##STR89## NHCOCH.sub.3
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
166
" " H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
167
" " H C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
168
" " H C.sub.2 H.sub.5
4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
169
##STR90## NHCOCH.sub.3
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
170
" NHCOCH.sub.3
H C.sub.2 H.sub.5
4-CH.sub.3
"
171
" NHCOCH.sub.3
H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
172
" NHCONH.sub.2
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
173
" " H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
174
" " H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
175
##STR91## NHCONH.sub.2
H C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
176
##STR92## NHCONH.sub.2
H C.sub.2 H.sub.5
4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
177
" NHCONH.sub.2
H C.sub.2 H.sub. 5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
178
" NHCONH.sub.2
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
179
" NHCONH.sub.2
H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
180
" NHCOCH.sub.3
H C.sub.2 H.sub.5
H 4-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
181
" NHCOCH.sub.3
H C.sub.2 H.sub.5
4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.4 OSO.sub.3
H
182
" NHCOCH.sub.3
H C.sub.2 H.sub.5
4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.5 OSO.sub.3
H
183
" NHCOCH.sub.3
H H 4-CH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.5 OSO.sub.3
H
184
" NHCOCH.sub.3
H H 4-OCH.sub.3
3-CH.sub.2 SO.sub.2
C.sub.2 H.sub.5 OSO.sub.3
H
__________________________________________________________________________
The table examples are characterised by the following .lambda..sub.max values (H.sub.2 O):
______________________________________
Example nm
______________________________________
3 518, 540
4 518, 540
7 519, 540
8 518, 540
21 521, 545
34a 521, 544
44 519, 540
53 486
54 486
56 485
66 483
66a 482
66b 483
78 502
78b 501
78c 502
79 503
80 501
82 497
86 513
87 514
88a 512
95 389
96 390
97 389
100 389
105 388
106 388
107 388
108 387
111 397
112 399
113 397
114 396
115 400
116 416
117 416
118 416
119 416
120 418
135 388
136 389
137 388
138 388
147 390
148 390
151 407
152 407
172 397
165 388
166 388
167 388
171 399
173 417
174 418
175 388
177 388
179 389
______________________________________
Claims
1. Reactive dyestuff which, as the free acid, has the formula ##STR93## in which K is ##STR94## the bonding to the triazinyl radical taking place in each case via the amino function of K,
- Y denotes CH.dbd.CH.sub.2, CH.sub.2 CH.sub.2 OSO.sub.3 H or CH.sub.2 CH.sub.2 Cl,
- R denotes H or C.sub.1 -C.sub.3 -alkyl, which may be substituted by OH, CO.sub.2 H or CN,
- Z denotes H, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy,
- D denotes a phenyl or naphthyl radical substituted by SO.sub.3 H, CO.sub.2 H, CH.sub.2 --SO.sub.2 W, SO.sub.2 W, NH-COCH.sub.3, C.sub.1 -C.sub.4 -alkyl and/or C.sub.1 -C.sub.4 -alkoxy, W having one of the meanings given under Y, or denotes a radical of the structure ##STR95## A denotes H, C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkoxy, B denotes H, C.sub.1 -C.sub.4 -alkyl, halogen, C.sub.1 -C.sub.4 -alkoxy, --OH, SO.sub.3 H-- or OSO.sub.3 H-substituted C.sub.1 -C.sub.4 -alkyl, NHCONH.sub.2, NHCO-(-C.sub.1 -C.sub.4 -alkyl), NHCOCH.sub.2 OSO.sub.3 H, NHCO-(--CH.sub.2 --).sub.1-3 SO.sub.3 H, NHCOCH.sub.2 OH or NHCO-(--O-C.sub.1 -C.sub.4 -alkyl).
2. Reactive dyestuff according to claim 1, of the formula ##STR96## in which R, Y, A, B and Z have the meaning given in claim 1, and the phenyl or naphthyl radical D can be additionally substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, NHCOCH.sub.3, CH.sub.2 SO.sub.2 W or SO.sub.2 W, W having one of the meanings given under Y.
3. Reactive dyestuff according to claim 1 of one of the following formulae ##STR97## in which X is H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.2 SO.sub.2 W or SO.sub.2 W,
4. Reactive dyestuff according to claim 1 of one of the following formulae ##STR98## in which V denotes H, CH.sub.3, OCH.sub.3, OC.sub.2 H.sub.5 or NHAcyl, in particular NH--CO--CH.sub.3,
- p,m, independently of one another, denote 0 or 1,
- R denotes H or C.sub.2 H.sub.5,
- W,Y, independently of one another, denote CH.dbd.CH.sub.2 or CH.sub.2 CH.sub.2 OSO.sub.3 H, and
- Z denotes H, CH.sub.3 or OCH.sub.3.
5. Reactive dyestuff according to claim 1, characterised in that
- A is H,
- B is CH.sub.3, OCH.sub.3, NHCOCH.sub.2, NHCONH.sub.2 or NHCOCH.sub.2 OSO.sub.3 H,
- R is H or C.sub.2 H.sub.5,
- W and Y, independently of one another, are CH.dbd.CH.sub.2 or CH.sub.2 CH.sub.2 OSO.sub.3 H and
- Z is H, CH.sub.3 or OCH.sub.3.
6. Reactive dyestuff according to claim 1 of the formula ##STR99## where R.sup.1 is CH.sub.3 or NH.sub.2.
7. Reactive dyestuff according to claim 1 of one of the following formulae ##STR100##
8. Process for the dyeing or printing of natural and synthetic OH- and/or amido-containing materials, in which a dye is applied to the material or incorporated in the material and fixed, if appropriate in the heat and/or in the presence of an acid-binding agent, characterised in that the dyestuff used is a dyestuff according to claim 1.
| 0065732 | December 1982 | EPX |
| 0079562 | May 1983 | EPX |
| 0085025 | August 1983 | EPX |
| 0085654 | August 1983 | EPX |
| 0094055 | November 1983 | EPX |
| 0307817 | March 1989 | EPX |
| 0356681 | March 1990 | EPX |
| 46-41432 | December 1971 | JPX |
| 9109914 | July 1991 | WOX |
- Abstract of JP 91-055513 (Aug. 1991). Abstract of JP 1-104,661 (Apr. 1989). Abstract of JP 92-10508 (Feb. 1992). Abstract of JP 92-24391 (Apr. 1992).
Type: Grant
Filed: Nov 24, 1992
Date of Patent: Jun 27, 1995
Assignee: Bayer Aktiengesellschaft (Leverkusen)
Inventors: Karl-Josef Herd (Odenthal-Holz), Thomas Eizenhofer (Cologne), Wolfgang Harms (Odenthal), Manfred Hoppe (Kuerten), Wolfram Reddig (Bergisch Gladbach)
Primary Examiner: Mary C. Lee
Assistant Examiner: Fiona T. Powers
Law Firm: Sprung Horn Kramer & Woods
Application Number: 7/982,171
International Classification: C09B 6208; C09B 62507; D06P 138;
